Process for treating proteinaceous and cellulosic materials with perfluoroguanamines



United States Patent PROCESS FOR TREATING PROTEINACEOUS AND CELLULUSIC MATERIALS WITH PERFLUORO- GUANAMINES John T. Shaw, Middlesex, N.J., assignor to American Cyanamid Company, Stamford, Conn., a corporation of Maine No Drawing. Uriginal application Dec. 24, 1958, Ser. No. 782,640. Divided and this application Sept. 9, 1963, Ser. No. 316,790

7 Claims. (Cl. 11714l) This application is a divisional application of Serial No. 782,640 filed December 24, 1958, and now abandoned.

This invention relates to a novel class of guanamines and more particularly to perfluoroguanamines and the method of preparing the same. In addition, the present invention relates to the application of the above-said novel perfluoroguanamines to various bases, and in particular, bases of proteinaceous or cellulosic origin to achieve a number of desirable effects, including insect repellency and the provision of germicidal, grease and oil resistance to such bases.

The perfiuoroguanamines of this invention may be dewhere n may be an integer between -1 and 14, m is an integer between 0* and 9, and R to R are selected from the group consisting of H, alkyl, cycloalkyl, allyl, phenyl, substituted phenyl, or CH OR wherein R is H or lower alkyl containing 1 to 4 carbon atoms.

As indicated by the above general references to the perfluoroguanamines contemplated by this invention, the term perfluoroguanamines includes perfluoroguanamines per se, their formaldehyde condensates, or methylol guanamines, and the alkylated or etherified perfiuoroguanamine-formaldehyde condensates or methylol guanamines.

The use of certain guanarnines and derivatives thereof as textile finishing resins has been recognized and they have been employed to achieve a wide variety of effects on textile materials, as for example the impartation of crease resistance thereto. As a typical illustration of this prior art, reference is made to U.S. Patent No. 2,385,766.

An object of the present invention is to provide a novel class of perfluoroguanamines, as that term is herein-above identified, and a novel process for the preparation of said perfluoroguanamines.

A further object of this invention is to provide a process for the preparation of perfluoroguanamines contemplated by this invention, which process is not applicable to the preparation of other corresponding perhaloguanamines, as for example, per-chloro or perbro-moguanamine compounds.

A further object of this invention is to provide a process for treating base materials, such as proteinaceous or cellulosic base materials, to impart a number of desirable effects thereto, including insect repellency, grease and oil repellency, germicidal activity, and with respect to cellulosic textile materials, such properties as crease resistanoe and shrinkage control.

A still further object of the present invention is to provide base materials of proteinaceous or cellulosic origin characterized by the above-enumerated and other desirable properties.

THE PERFLUOROGUANAMINES OF THIS INVEN- TION AND THEIR METHOD OF MANUFACTURE The perfluoroguanamines of this invention may be defined by the following general formulas:

wherein n is an integer between 1 and 14, inclusive, m is an integer between 0 and 9, inclusive, and R to R are hydrogen, alkyl, cycloalkyl, allyl, phenyl, or substituted phenyl.

As typical illustrations of the perfluoroguanamines of this invention, the following are illustrative:

trifluoroacetoguanamine, N-ethyl-trifiuoroacetoguanamine, N-n-butyl-trifiuoroacetoguana'mine, N-n-decyl-trifiuoroacetoguanamine, N-n-octadecyl-trifluoroacetoguanamine, N-cyclohexyl-trifiuoroacetoguanamine, N-phenyl-trifiuoroacetoguanamine, N,N-diethyl-trifluoroacetoguanamine, N,N'-bis (p-chlorophenyl) -trifluoroacetoguanamine, (Formula I where n=0), pentafluoropropioguanamine, N-n-butyl-pentafluoropropioguanamine, (Formula I where 21:1), heptafiuorobutyroguanamine, N-ethyl-heptafiuorobntyroguanamine nonafiuorovalerioguanamine (I, 12:3), undecafiuorocaproguanamine, (I, 2 pentadecafiuorocapryloguanamine, nonadecafiuorocapriguanamine, heptacosafluoromyristoguanamine, hexafluoroglutaroguanamine, N,N"-di-n-butyl-hexafluoroglutaroguanamine, N,N,N",N-tetrakis(p-chlorophenyl)-hexafiuoroglutaroguanamine, (Formula II where 111:3), and hexadecafiuorosebacoguanamine and N,N"-idiphenyl-hexadecafiuorosebacoguanamine, (II, m=8).

These and the other perfiuoroguanamines contemplated by this invention may be converted to methylol perfiuoroguanamines by employing procedures normally involved in the methylolation of an aminoplast with aldehydes, and more specifically, with formaldehyde or formaldehyde-engendering substances such as paraformaldehyde, hexamethylene tetramine, and other known equivalents. To achieve methylolation (the condensation of the perfluoroguanamine with formaldehyde) a suitable perfiuoroguanamine is reacted at an alkaline pH usually from between about 7.5 and 10, with from between about 1 and about 9 moles of formaldehyde, depending upon the number of available hydrogens and extent of methylolation or condensation desired. Thus, it will be noted that the perfiuoroguanamines typified by general Formulas I and II above, if not substituted, contain four replaceable hydrogens (Formula I) or 8 replaceable hydrogens (Formula II) prior to methylolation. Normally, a slight excess of the formaldehyde is required to achieve a given or desired degree of methylolation. Thus, for example, if it is desirable to produce the monomethylol derivative, from between 1 and 2 moles of formaldehyde should be employed. If complete methylolation is desired, a slight excess of formaldehyde over that required to achieve full methylolation is employed. In methylolating the perfiuoroguanamines in accordance with this invention, temperatures on the order of from between about 30 C. to 100 C. may be employed, and preferably temperatures from between about 35 up to about 85 C. are most effective. In general, methylolation may be considered to be complete when the solution clears.

To a degree, the amount of methylolation to be achieved or required is dependent upon end use. Where it is only necessary to provide a means of attachment of the guanamine molecules to a fiber, as for example, in rnoth proofing or grease proofing of the fiber or fabric formed therefrom, a monomethylol derivative of the guanamines contemplated by this invention is for the most part suitable. However, where the methylol perfiuoroguanamine is to be employed to impart crease proofing or shrinkage control to the base material, as for example, a cellulosic fabric, in addition to imparting certain of the special properties identified above, two or more methylol groups are required.

As examples of suitable methylol perfiuoroguanamines within the purview of the present invention, the following are illustrative: trimethylol trifluoroacetoguanamine; tetramethylol trifluoroacetoguanamine; trimethylol pentafiuoropropioguanamine; tetramethylol pentafluoropropioguanamine; tetramethylol heptafluorobutyroguanamine; tetramethylol nonafluorovaleroguanamine; trimethylol pentadecafluorocapryloguanamine; tetramethylol nonadecafiuorocapriguanamine; tetramethylol heptacosafluoromyristoguanamine; hexamethylol tetrafluorosuccinoguanamine; octamethylol hexafiuoroglutaroguanamine; octamethylol hexadecafluorosebacoguanamine; trimethylol N-ethyl-trifluoroacetoguanamine; trimethylol N-nbutyl-trifiuoroacetoguanamine; dimethylol N-cyclohexylpentafluoropropioguanamine; trimethylol N-phenyl-heptocosafluoromyristoguanamine; dimethylol N,N'-diethyltrifluoroacetoguanamine; tetramethylol N,N"-di-n-butylhexafluoroglutaroguanamine; methylol N,N-diethyl-trifiuoroacetoguanamine; and dimethylol N,N-diethyl-trifluoroacetoguanamine.

The methylol perfiuoroguanamines of this invention may be etherified or alkylated by employing known methods usable in the etherification of methylol aminoplast resins. In general, alkylation or etherification is carried out on the acid side, where the methylol perfiuoroguanamine is reacted with a saturated monohydric aliphatic alcohol containing from 1 to 4 carbon atoms. The amount of alcohol required to achieve a given degree of etherification depends upon the degree of etherification desired and the number of moles of combined formaldehyde or methylol groups in the perfiuoroguanamine molecule. In general, a slight molecular excess of the selected alcohol should be employed to achieve etherification of a combined mole of formaldehyde. Thus, for example, where the perfiuoroguanamine contains two methylol groups, and it is desired to fully etherify these groups, from between 2 to 3 moles of alcohol should be employed.

Normally, etherification may be carried out at temperatures from between about 30 C. to 100 C., and preferably from between 35 to C., employing a pH of from between about 1 and about 6.

The reaction is carried out until etherification is complete, which is evidenced by the clearness of the solution, and thereafter, the pH of the solution is neutralized by adjusting to a pH of between 7 and 8 to prevent further reaction and polymerization. The methylol and alkylated methylol perfiuoroguanamines of the present invention are preferably water-soluble. The degree of solubility, in general, is determined by the number of methylol groups attached to the perfiuoroguanamine molecule and by the length of the perfiuoroalkyl chain in the molecule. In general, solubility is increased by increasing the number of methylol groups and by shortening the perfiuoroalkyl chain. The perfiuoroguanamines having less than complete solubility in water may be employed in aqueous dispersions, in water-alcohol mixtures, or in solution in organic solvents therefor.

It is generally preferred that the perfiuoroguanamines and their methylolated and alkylated methylol derivatives be in monomeric form for the utility to be described more fully hereinafter, or be only partially polymerized, since a high degree of polymerization adversely affects the water solubility of these materials.

As examples of suitable alkylated methylol perfiuoroguanamines within the purview of the present invention, the following are illustrative:

tris(methoxymethyl) trifluoroacetoguanamine;

tetrakis(methoxymethyl) trifluoroacetoguanamine;

tris(methoxymethyl) methylol pentafluoropropioguanamine;

tetrakis(ethoxymethyl) heptafluorobutyroguanamine;

bis(methoxymethyl) bis(ethoxymethyl) pentadecafiuorocapryloguanamine;

tris(methoxymethyl) butoxymethyl heptacosafluoromyristoguanamine;

bis(eth0xymethyl) hexamethyl hexafluoroglutaroguanamine;

N,N,N-tris(methoxymethyl)-N-ethyl-trifiuoroacetoguanamine;

N,N-bis(methoxymethyl)-N-methylol-N'-ethyl-trifiuoroacetoguanamine;

N,N-bis (methoxymethyl) -N-n-butyl-trifiuoroacetoguanamine;

N-methoxymethyl-N'-ethyl-pentafiuoropropioguanamine;

N,N-bis(ethoxymethyl) -N',N '"-di-n-butyl-hexafluoroglutaroguanamine.

The perfiuoroguanamines per se, from which the methylolated and alkylated methylol derivatives may be derived, are prepared, in general, by reacting an ester of a perfiuoroalkyl carboxylic acid with a biguanide. In general, and preferably, esters are lower alkyl esters, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like, but the present invention is in nowise limited thereto. In the preparation of the perfiuoroguanamines per se, a suitable perfiuoroalkane carboxylic acid ester is reacted with a biguanide, normally and preferably using a slight excess of the ester. The reaction is carried out at a temperature of from between 15 C. and C. and preferably from between 35 and 65 until the guanamine is formed, which is generally indicated by the formation of a precipitate. The resulting precipitate is then filtered off and dried, or it may be condensed with formaldehyde and etherified, in accordance with the general procedure outlined above.

As will be seen more clearly hereinafter, the above.

generally described process is not suitable for the preparation of such perhalo guanamines as tribromo and trichloroactoguanamine. In this connection, methyl trifluoroacetate and biguanide will produce trifluoroacetoguanamine, but methyl tribromoacetate or methyl trichloroacetate and biguanide do not produce the corresponding trihaloacetoguanamine. Reasons for this distinction are not known.

The perfluoroalkane carboxylic acids used as the starting material in the preparation of the esters and diesters employable in the process of this invention are wellknown and are described in U.S. Patents No. 2,657,011 and No. 2,693,458, while the perfluoro dicarboxylic acids are disclosed in U.S. Patent No. 2,715,107 and in Indus trial and Engineering Chemistry, 39, at page 415. The preparation of the esters of these perfiuorocarboxylic acids may be accomplished in accordance with standard procedures well known to those skilled in the art, which means will be exemplified in the following examples.

Biguanides per se and N-substituted biguanides are generally well known, preparation of the latter being described in the literature, e.g., Monat. 9, 228 (1888); Ber., 62, 1394 (1929); Ber., 62, 1400 (1929). Among the N-substituted biguanides which may be employed, the following are illustrative: l-methylbiguanide; l-ethylbiguanide; l-n-propylbiguanide; l-isopropylbiguanide; l-nbutylbiguanide; l-isobutylguanide; 1-sec.-buty1biguanide; l-n-hexylbiguanide; 1-sec.-octylbiguanide; l-n-decylbiguanide; l-n-dodecylbiguanide; 1-n-octadecylbiguanide; 1- cyclohexylbiguanide; l-allylbiguanide; l-phenylbiguanide; 1-(p-chlorophenyl)biguanide; 1,5-diethylbiguanide; 1,5- bis(p-chloropheny1)biguanide; and 1,1-diethy1biguanide.

While, in general, the present invention has been described with respect to guanamines with saturated straight chain perfluoroalkyl or alkylene groups, guanamines with branched chain or unsaturated perfiuoroalkyl or alkylene groups are also contemplated.

In order to illustrate the present invention, the following examples are given primarily by way of illustration. No details contained therein should be construed as limitations on the present invention, except insofar as they appear in the appended claims. All parts are by weight unless otherwise designated.

l-NIH Eight parts (0.0562 mole) of ethyl trifluoroacetate was added portionwise with stirring to a solution of 5.1 parts (0.051 mole) of biguanide is 18 parts of methanol at 35 C. The rate of addition was such that the solution boiled very gently. A precipitate formed, and after stirring for 48 hours at room temperature, the precipitate was filtered off and dried. The product, a white solid, weighed 6.2 parts and sublimed at 318-323 C. (Recrystallization of the product from methanol gave no improvement in the sublimation point.)

Analysis.Calcd. for C H N F C, 26.8; H, 2.25; N, 39.1. Found: C, 26.8; H243; N 39.8.

Example 2.-Trz'fluor0acetoguanamine The methyl trifluoroacetate used in this example was prepared by mixing 100 parts (0.968 mole) of concentrated sulfuric acid and 56 parts (1.76 moles) of absolute methanol in the cold and adding at 05 C. 100 parts (0.88 mole) of trifluoroacetic acid over a period of 1 hour with stirring. After standing overnight, the mixture was stirred for 2 hours while refluxing. The resulting solution, after cooling to room temperature and drying over anhydrous calcium sulfate for 30 minutes, was distilled in the presence of parts of phosphoric 6 anhydride. 82 parts (73.5%) of methyl trifiuoroacetate boiling at 4344 C. was obtained.

To a solution of 58.7 parts (0.582 mole) of biguanide in 230 parts of absolute methanol, prepared at 50 C. and cooled to 35 C., there was added 82 parts (0.64 mole) of methyl trifluoroacetate over a period of 90 minutes. The mixture, after stirring overnight at room temperature, was cooled to 5 C. and filtered. The product, weighing 93.4 parts after drying in vacuo (89.9% of theory), sublimed at 318-3215 C.

Example 3.-P0Zymethyl0l trifluoroacetoguanamine Ten parts (0.055 mole) of trifluoroacetoguanamine was added portionwise to 17.8 parts of a 37% .solution of formaldehyde, containing 6.6 parts (0.22 mole) of formaldehyde, with the pH adjusted to 11.6 with sodium hydroxide. The mixture was heated at -80 C. for 30 minutes in order to obtain a complete solution. Analysis of this solution showed that 3.5 moles of formaldehyde had reacted with the guanamine.

Example 4.-Pentafluoropropiogaanamine o F to Fa The methyl pentafluoropropionate used in this example was prepared by adding dropwise 34 parts (1.06 moles) of methyl alcohol to a mixture of 49 parts (0.5 mole) of concentrated sulfuric acid and 164 parts (1.0 mole) of pentafiuoropropionic acid at 0 C. After refluxing for 19 hours the product was distilled twice in the presence of phosphoric anhydride. The distillate, boiling at 60-61.5 C., weighed 107 parts (60.9% of theory).

To a solution of 15.1 parts (0.15 mole) of biguanide in 48 parts of absolute methanol at 35 C., there was added portionwise with stirring 30.8 parts (0.173 mole) of methyl pentafiuoropropionate. After stirring for 3 hours at room temperature, the reaction mixture was cooled and the precipitate was filtered off. The product, after washing with a little methanol and drying, weighed 25 parts (72.7% of theory) and melted at 255-257 C. Crystallization of the product from methanol did not result in a higher melting point. (In another preparation by the same method, the yield was of theory.)

Example 5.P0lymetlzyl0l penlafluoropropioguanamine To a solution (30.5 parts) of 37% formaldehyde, containing 11.2 parts (0.372 mole) of formaldehyde, with the pH adjusted to 11.5 with sodium hydroxide, there was added 21.0 parts (0.093 mole) of pentafluoropropioguanamine. After heating at 7080 C. for 30 minutes, an analysis of the solution indicated that 3.8 moles of formaldehyde had reacted with each mole of guanamine.

The methyl heptafluorobutyrate used in this example was prepared by adding a mixture of 64 parts (2 moles) of methanol and parts 1.1 moles) of concentrated sulfuric acid at 5 C. to 214 parts (1.0 mole) of heptafluorobutyric acid also at 5 C. The reaction mixture was stirred while allowing to warm to room temperature and for an additional 4 hours at room temperature, followed by standing overnight. After refluxing for 2 hours, distillation of this material gave 210.5 g. of liquid boiling at 70-80 C. The product, after redistill- 7 ing in the presence of phosphoric anhydride, weighed 196 g. and boiled at 8081 C.

68.4 parts (0.3 mole) of methyl heptafluorobutyrate was added to a solution of 26.2 parts (0.26 mole) of biguanide in 68 parts of absolute methanol at 35 C. The rate of addition was such that a gentle boil was maintained. After stirring for 48 hours at room temperature, the reaction mixture was cooled and the precipitate was filtered off and dried. The product weighed 45.7 g. and melted at 202204 C. Concentration of the mother liquor gave an additional amount of 9.0 parts, or a total yield of 75.6% of theory.

Analysis.--Calcd. for C H4F7N5i C, 25.8; H, 1.44; N, 25.1 Found: C, 26.0; H, 1.64; N,25.2.

Example 7.Polymethylol heptafluorobutyroguanamfne 13.5 parts (0.0484 mole) of heptafluorobutyroguanamine was added portionwise over minutes to 17.8 parts of 37% solution of formaldehyde, containing 6.6 parts (0.22 mole) of formaldehyde, with the pH adjusted to 11.6 with sodium hydroxide. After heating at 80 C. for 30 minutes, the reaction mixture, which separated into two layers, was evaporated in vacuo to remove the water. The residue, a clear viscous liquid, was analyzed for combined formaldehyde. The result indicated that 3.58 moles of formaldehyde had reacted with each mole of guanamine.

Example 8.Pentadecafluorocapryloguanamine (i F2)GC a The methyl pentadecafiuorocaprylate required for this example was prepared by adding 103.5 parts (0.25 mole) of pentadecafluorocaprylic acid portionwise to a mixture of 32 parts (0.326 mole) of concentrated sulfuric acid and 16 parts (0.5 mole) of methanol while keeping the temperature at 5 C. After stirring for two hours at room temperature, the resulting emulsion was allowed to stand overnight and was then refluxed for two hours. On cooling, two layers formed, and the lower layer was separated and distilled in the presence of 16 parts of sulfuric acid. The fraction boiling at 157160 C. was redistilled in the presence of phosphoric anhydride. The desired ester, boiling at 157158 C., weighed 56 g. (52.3% of theory).

42.8 parts of methyl pentadecafluorocaprylate (0.1 mole) was added portionwise to a solution of 9.1 parts (0.09 mole) of biguanide dissolved in 32 parts of absolute methanol, with the temperature rising from 35 to 56 C. while cooling in an ice bath. When about one-half of the ester had been added, it was necessary to add 55 parts of methanol in order to maintain a stirrable mixture. After stirring overnight, the precipitate was filtered off, and the filter cake was washed with methanol. The dried product weighed 20.8 parts and melted at 177l79 C. Concentration of the mother liquor gave an additional 5.5 parts, a total yield of 79.5% of theory.

Analysis.--Calcd. for C H F N C, 25.0; H, 0.80; N, 14.6. Found: C, 25.0; H, 1.37; N, 14.7.

Example 9.-N0nadecafla0r0capriguanamine This example was carried out as in Example 8, substituting equal moles of nonadecafiuorocapric acid for the 0 methyl pentadecafluorocaprylate.

Example 1 1.Hexafluoroglutaroguanamine 5.31 parts (0.0198 mole) of dimethyl hexafluoroglutarate was added at room temperature over a 5-10 minute period to a solution of 3.21 parts (0.32 mole) of biguanide in 40 parts of methanol. Stirring was continued for one hour at room temperature and for 1.5 hours at the reflux temperature. After cooling in an ice-water bath, the white precipitate was filtered off and washed. The product weighed 5 parts and melted above 320 C.

Example 12.Hexadecafluorosebacoguanamine As in Example 11, substituting equal moles of dimethyl hexadecafiuorosebacate for the dimethyl hexafiuorogluta-rate.

Example 13.--N-nButyl-trifluoroacetoguanamine i F3 C To a solution of 3.86 parts (0.02 mole) of l-n-butylbiguanide hydrochloride and 1.18 parts (0.02 mole) of sodium methoxide in 60 parts of methanol there was added 2.76 parts (0.022 mole) of methyl trifluoroacetate. After stirring for four days at room temperature, the solution was poured into about parts of water. The precipitate was filtered off, and after drying, it weighed 2.75 parts and melted at 98-100" C.

Analysis.Calcd. for C H F N C, 40.9; H. 5.14; N, 29.8. Found: C, 41.1; H, 5.19; N, 29.6.

Example 14.N-ethyl-trifluoroaceloguanamine The method of Example 13 is used, substituting 3.30 parts (0.02 mole) of l-ethylbiguanide hydrochloride for the l-n-butylbiguanide hydrochloride.

Example 15.-N-n-ctadecyl-triflaoroaceloguanamine The method of Example 13 is used, substituting an equivalent quantity of l-n-octadecylbiguanide hydrochloride for the l-n-butylbiguanide hydrochloride.

Example 16.--N-cycl0hexyl-trifluoroacetoguanamine (IJFa C 15 ll I rfir CH2CH2 H2NC\ /GNHCs2 CH;

GET-CH2 The method of Example 13 is used, substituting 4.3 parts (0.02 m.) of l-cyclohexylbiguanide hydrochloride for the l-n-butylbiguanide hydrochloride.

Example 17.N-phenyl-trifluoroacetoguanamine (I113 0 l H2N-C CNH'CBH5 A mixture of 10.8 parts (0.033 m) of 1,5-bis(p-chlorophenyl) biguanide, 8.5 parts (0.066 mole) of methyl trifluoroacetate, 1.6 parts (0.039 mole) of sodium methoxide and 120 parts of methanol was heated at 100 C. in an autoclave for 24 hours. After the reaction mixture was cooled and poured into about 200 parts of water, the precipitate was separated by filtration and dried. The product, after purification by crystallization from dioxane, melted at 182-185 C.

Analysis.-Calcd. for C1H1QC12F3N5 C4H202: C, 49.2; H, 3.75; Cl, 14.5; N, 14.5. Found: C, 49.1; H, 3.55; C1, 14.6; N, 14.3.

glataroguanamine 0 o t t i orrxomx-rrrr-o C-NHz H2N-C o-Nnomxorn The method of Example 13 is used, substituting 2.95 parts (0.011 mole) of dimethyl hexafluoroglutarate for the methyl trifiuoroacetate.

1 0 Example 20.Tribromoacetoguanamine C B 1'3 6 N% \N HzN-( -NHz This is a known compound and the procedure used in its preparation is found in the literature: Centralblatt 2, 1359 (1905).

An attempt to prepare this compound by reacting biguanide with tribromoacetate by the procedure outlined in Example 1 was not successful. The products formed This compound is known and the procedure used in its preparation is described in British Patent 642,409 (American Cyanamid). An attempt to prepare this compound by reacting biguanide with methyl trichloroacetate by the procedure of Example 1 was not successful. The compounds which were formed were not identified.

THE TREATMENT OF BASES WITH THE PER- FLUOROGUANAMINES OF THIS INVENTION The perfluoroguanamines of this invention, including the methylolated and alkylated methylolated derivatives thereof, may be applied to suitable bases, primarily those of a proteinaceous or cellulosic characteristic, to impart a wide variety of effects. In general, depending upon the nature of the base and the solubility characteristic of the guanamine, they may be applied from aqueous, wateralcohol or solvent solutions, or aqueous dispersions by spraying, immersion, dipping, padding, or the like.

In general, the perfluoroguanamines of this invention may be applied to fibers of either a proteinaceous or cellulosic origin or the materials formed therefrom, such as textile fabrics, woven or non-woven, including felted, Wood, paper, or cellulosic films.

With respect to proteinaceous bases, suitable examples of these include wool fibers and fabrics formed therefrom, furs, feathers, hair, hides and numerous other materials which may be treated alone or blended with nonproteinaceous materials, such as cellulosics, synthetic fibrous materials, such as nylons, acrylics, and the like. In general, the application to proteinaceous base materials of the perfluoroguanamines of this invention is for the purpose of imparting insect repellency, grease and oil resistance or repellency thereto.

In general, the application to cellulosic base materials is for the purpose of imparting grease and oil repellency thereto, as well as for the purpose of imparting dimensional stability and crease resistance, as in the case of cellulosic textile materials. Additionally, with respect to textile materials, the perfluoroguanamines of this invention may be employed as hand modifiers.

For purposes of illustrating certain of the use aspects of the compounds, their methylol derivatives and their alkylated methylol derivatives in accordance with the present invention, the method of imparting some or all of the characteristics identified above to textile materials will be described.

By textile materials as that and similar terms are employed herein, it is :meant filaments, yarns, fibers and fabrics, whether the latter be felted, woven or nonwoven or otherwise formed.

By the term cellulosic material as that and similar terms are employed herein, it is means textile materials containing a substantial portion of cellulosic fibers, preferably at least 50%, such as cotton, regenerated cellulose, such as viscose, rayon, linen, hemp, jute, and the like. Such fibers may be used alone or blended with synthetic or natural textile materials, as for example, the nylons, the acrylic fibers, polyester fibers, wool fibers, silk and the like.

In the application of these resinous compounds to textile bases, they may be applied as solutions or dispersions by any of the several known methods for finishing textile materials. Thus, they may be applied by spraying, immersion, dipping, padding, or the like, the latter being the usually preferred and more conventional method. For the unmethylolated guanamines or those that are water-insoluble, it is desirable to use an organic solvent, such as dimethyl formamide or methanol or the like, or a mixture of water and dimethyl formamide or an alcohol, such as methanol, ethanol, or mixtures thereof, in order to obtain a solution which may be padded onto the fabric. Alternatively, these compounds may be padded or applied from aqueous dispersions. The application baths or treating solutions or dispersions may normally contain from 0.1 to 30% by weight of guanamines solids and preferably from between about 0.5 to about Curing catalysts are normally employed with the methylolated guanamines and their alkylated derivatives to provide a desirable rapid cure of the resins on the fiber. Among the curing catalysts that may be employed are the ammonium salts, such as ammonium chloride, amine salts like triethylamine hydrochloride, alkanolamine salts, like triethanolamine hydrochloride, metal salts, such as magnesium chloride, zinc nitrate or aluminum chloride, and the like, free acids, like oxalic, tartaric, and the like. These materials may be employed singly or in combination with one another. Catalyst concentrations may vary widely, depending upon the effectiveness of the catalyst itself, and the intended use of the resin treated base material. The range may be from about .5 to 25%, and in certain limited instances higher, based on the weight of the resin solids employed. More particularly, with ammonium salts, such as ammonium sulfate, it may vary from about .5 to 7.5%, based on the weight of the resin solids employed; with metal salts such as magnesium chloride, zinc nitrate, amounts of between 8 and 20%, based on the weight of the resin solids is a preferred operating range. With amine or alkanolamine salts, such as isopropylamine hydrochloride, from about 1 to 10% catalyst concentration, based on the weight of the resin solids employed, is preferred.

As noted, the preferred method of treating textile materials, and specifically formed fabrics, consists of padding the material through a suitable pad bath, followed by passing the wet material through squeeze rolls adjusted to control the amount of pad bath liquor picked up by the textile material. Thereafter, the treated or impregnated textile material is dried and, if need be, the resin cured.

The drying and curing may be accomplished in separate steps, or in one operation, if this is preferred. When drying is carried out in a separate step, it may be done at temperatures ranging from about 100 to 250 F. for from about three minutes to about one and one-half minutes, respectively. These times and temperatures have been found to be eminently satisfactory, particularly for lightweight cellulosic fabrics. Heavier fabrics may require more time. Generally speaking, the length of time required is inversely proportional to the temperature at which drying is affected. Thus, somewhat longer periods of time will be required when lower temperatures are employed, and somewhat shorter periods of time will be required where higher temperatures are employed. Thereafter, curing of the resin on the treated fabric is carried out. Again, in general, the time required for the cure is inversely proportional to the temperature. The most preferred temperature and time range for the curing of dry fabrics are from about 4 minutes at about 275 F. to about 30 seconds at 450 F. When drying and curing are carried out in a single stage operation, times from between about 15 minutes at about 250 F. to about 3 minutes at about 350 F. have been found satisfactory. It should be noted that where the guanamines are unmethylolated, only drying is necessary to remove the carrier or solvent employed.

In general, it has been found that for the moth proofing of wool and related proteinaceous materials, and for the imparting antibacterial properties to cellulosic materials, guanamines containing short perfiuoroalkyl groups are best, and it appears that the preferred compound is trifluoroacetoguanamine.

For imparting grease and oil repellency, the guanamines containing long perfiuoroalkyl groups appear to be best, and thus the preferred members within the scope of this invention are those having the longest alkyl or alkylene groups.

In order that this aspect of the present invention may be more fully illustrated, the following examples are given primarily by way of illustration. No details or enumerations contained therein should be construed as limitations on the present invention, except insofar as they appear in the appended claims. All parts and percentages are by weight unless specifically designated otherwise.

Example 22.--Applicati0ns of perfluoroguanamincs on wool Solutions of certain of the perfiuoroguanamines described in Examples 1-12 and 20 and 21 hereinabove were padded onto wool flannel from a solvent solution so as to impart the sol-ids thereto indicated in Table I below. The fabric was then dried at 225 F.

1 DMF =Dimethyll'ormamide.

Mothproofing tests on wool treated with perfluoroguanamirzes The testing procedure was that recommended by the American Society of Testing Material with the following exception: black carpet beetles were of mixed age in the culture and the only practical method of selection was with 16 and 18 mesh US. Standard Sieves as described in the ASTM Manual (ASTM specifies larvae five months old and selected for uniform size by the above described procedure).

Ten larvae of the black carpet beetle (Attagenus piceus) were placed in a 4 petri dish with a 1%" circular disc of wool to be tested. There were four replicates per treatment. The test was held for 28 days at F. and 60% relative humidity with light omitted. The degree of protection was determined by three methods:

1) Larval mortality observation of number of dead larvae.

(2) Excrement weightthe excrement of the 10 larvae per petri dish was weighed to the nearest tenth milligram; all four replicates averaged, the weight of the excrement deposited by the unfed larvae subtracted and the 13 percent reduction over the untreated wool controls calculated.

(3) Visual observationall wool samples were observed under a binocular microscope, and the degree of feed- 14 and 160 ml. of a dry cleaning soap solution, prepared as described on p. 133, Note 2, of the above reference. The solvent was drained out of the apparatus and 2,300 ml. of fresh naphtha was added and the rotating was ing is described as follows: Trace-feeding on nap only; 5 continued for minutes. After centrifuging and teamlight-feeding on fibers, but none sheared; moderate mg to remove the solvent, the cloth was pressed. small holes but none lar er than Ms' severe-man and lar e holes a y M othproofing tests on wool treated wlth polymethylol c The headings A, B, C, etc., are defined in Table I. pelfluomguanammes The results of the impregnation described in Table I 10 The mothproofing tests were carried out by the prowere evaluated in accordance with the above test procedure of Example 22. The results are shown in Table cedure and the data therefrom recorded in Table II. III below:

TABLE II Average Excrement Percent Reduction of Visual Weight Per Replicate Excrement Deposited Percent Observation Minus the Average from Treated Wool of Larval of Feeding Excrement Weight of Over the Average Mortality Damage to the Unt'ed Larvae from Untreated Wool (40 larvae) Wool (in mgs.)

Trace Light: Trace Light. Moderate. Light-Mod.

Do. Severe. Mod.-

Severe. l.2 Severe. o

1 Average of two tests on untreated wool. 2 Unted larvae.

Fabrics A and A1 were dry cleaned and wet drycleaned by the procedures of Example 23, and then tested for insect .repcllency in a second series of tests. The results are shown in Table IIa Five percent solutions of polymethylol perfluoroguanamines in a mixture of ethyl alcohol and water, using sufficient alcohol to keep the solutions clear (about were applied to wool flannel. The catalyst used was 35% of ammonium sulfate on the weight of the resin solids in the bath and the pick-up from the pad bath was 100% on the weight of the fabric. This resulted in a 5% application on the weight of the fabric. The fabric was then dried and cured for 6 minutes at 290 F.

The dry cleaning operation was carried out in the Dynamic Absorption Tester described on page 146 of the 1957 edition of the Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists. The cloth to be cleaned (265-g. load) was rotated in the above apparatus with 2,000 m1. of petroleum naphtha (Varsol) for 20 minutes. After centrifuging and steaming to remove the solvent, the cloth was pressed.

The wet dry-cleaning operation was carried out in the same apparatus. The cloth to be cleaned was rotated for 20 minutes with 2,300 ml. of petroleum naphtha (A) Polymethylol trifluoroacetoguanamine (Example (B) Polymethylol pentafiuoropropioguanarnine (Example 5).

TABLE III Percent Reduction of Visual Number Excrement Deposited from Observation of Dry Treated Wool Over the of Feeding Oleanings Average from Untreated Damage to 0 Severe. 0 78. 5 Trace. 5 76.0 Do. 25 76.0 Do. 1 5 51. 6 Do. 5 80. 6 Do.

1 Wet dry-cleaning.

Example 24.Applicati0n of trifluoroacetogztanamine 011 wool followed by after-treatment with melamine resin acid colloid 5.9% solution of trifluoroacetoguanamine in dimethylformamide was applied to wool flannel. A pick-up from the pad bath of resulted in a 5% application on the weight of the fabric. After drying the fabric at 225 F. for 2 minutes, the fabric was passed through a pad bath containing 5.9% of an acid colloid of methylolated trimethylol melamine. The acid colloid was prepared by allowing a solution of parts of methylolated trimethylol melamine and 74 parts of acetic acid in sufi'icient water to give a final volume equivalent to 1000 parts of water to stand overnight. With an 85% pick-up, the application of the colloid was 5% on the weight of the fabric. The fabric was dried and cured for 15 minutes at 225 F.

The dry cleaning opeartion was carried out as described in Example 23.

The mothproofing tests were carried out by the procedure of Example 22. The results are shown in Table IV below.

Example 25.Applicatin 0 polymethylol trifluoroacetoguanamine on cotton A solution consisting of 5.88 parts of polymethylol trifluoroacetoguanamine, 0.71 part of zinc nitrate, 25 parts of methanol and sufficient water to make a total of 100 parts was padded onto 80 x 80 cotton percale with 85% pick-up on the weight of the fabric. The (fabric, containing of the resin was dried at 225 F. for 2 minutes and cured at 350 F. for 1.5 minutes.

The wrinkle recovery was measured on a Monsanto Wrinkle Recovery Tester following the tentative test method 66 1956 described on page 158 of the 1957 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists, volume 33.

The washes under Wrinkle Recovery in Table VI were carried out at 212 F. by the procedure described under Test Method 14-1953 on page 123 of the above reference, using a Najort washer.

The yellowing index is calculated by the equation:

Yellowing index 7()( 1 51 E R577 The results of these tests are shown in Table V.

TABLE V Wrinkle Recovery Yellowing Index Initial 5 Washes Initial 9 Washes 25 Washes Untreated- 146 164 1. 4 1. 0 1. 0 Treatcd 252 239 2. 2 0.6 1. 4

These results show that cotton fabrics treated with polymethylol trifluoroacetoguanamine have good wrinkle recovery with no yellowing after repeated washes with chlorine present.

Example 26.Applicati0n 0f perfluoroguanamines on colton as germicides 1% applications of the perfluoroguanamines identified in Table VI were made on 80 x 80 cotton percale from a solution of dimethyl formamide. The fabrics were dried at 225 F.

The treated fabrics were tested for antibacterial activity by a standard agar plate method. This test is a convenient method for evaluating the extent of durability of the antibacterial activity of the textile finish, and involves the determination of the inhibition of the bacterial growth on a piece of textile placed on an agar plate inoculated with various strains of bacteria. The two commonly used strains are E. coli and S. aureus, which are strains usually employed in evaluation of antibacterial agents for various purposes.

Thus, by determining the antibacterial activity of cloth treated by the process of this invention before and after a number of laundering treatments, the effectiveness of the finish may be determined. Durability of the finish is determined by subjecting the treated textile to a series of repeated launderings. The number of times the material may be laundered before antibacterial activity decreases below an effective level will give a measure of the durability of the finish.

In the test for antibacterial activity, discs of treated fabric of a certain size (11.5 millimeters in diameter) are placed on an agar plate inoculated with the bacterial culture. After two hours contact, the disc is removed and the agar plate is incubated overnight. The degree of inhibition of growth gives an index of the inhibitory effect of the finish on the cloth. This inhibition is easily observed, since the areas where the bacterial growth is inhibited remains clear, whereas the remainder of the area where the bacterial growth has taken place becomes cloudy or opaque. The area under the disc is observed, and in addition, the total diameter of the area larger than that occupied by the disc is observed.

Effective finishes show clear area at least under the disc, with more effectively finished areas having a diameter greater than that of the disc itself. If the area of inhibition is greater than the area of the disc, the activity is given as the diameter of the clear area in millimeters. Otherwise, a rating of C denotes complete inhibition of bacterial growth under the disc; a rating of P denotes partial inhibition; and N denotes no inhibition or activity when S and VS deote slight and very slight inhibition. It should be noted that P is at least 50 to 75% inhibition under the test fabric.

The results are shown in Table VI below.

TABLE VI Zone of Inhibition E. coli S. aureus Trifiuoroacetoguanamine 12.0. Pentafiuoropropioguanamine N P-C. Pentadecafiuorocapryloguanamine V Example 27 .A pplication of pentadecafluorocapryloguallamine on cotton for oil repellency Example 28.-Applicati0n of polymethylol pentadecafluorocapryloguanam ine on cotton for oil repellency A solution consisting of 5.88 parts of polymethylol pentadecafluorocapryloguanamine, 0.71 part of magnesium chloride, 35 parts of ethanol and sufficient water to make a total of 100 parts, was padded onto cotton percale with an pick-up on the weight of the fabric. The fabric, containing 5% of the resin, was dried for 2 minutes at 225 F. and cured for 1.5 minutes at 350 F.

There was initial water repellency and oil repellency, the latter lasting for 30 minutes (up to 2 hours in some areas of the treated fabric). There was no fire Tetardancy. The wrinkle resistance (total W F in degrees) was 196.

As illustrated in Example 24, a perfiuoroguanamine of this invention may, where desirable, be employed with other conventional textile resins to achieve additional effects. Thus, for example, where the guanamine contains no functional groups capable of reacting with the textile material, it may be desirable to employ the guanamines with other textile finishing resins, and more particularly, aminoplast textile finishing resins.

Prominent among this class of materials are the polymethylolated melamines, including those melamines having from 2 to 6 moles of combined form-aldehyde which may also have been condensed with from 2 to 6 moles of alcohol, preferably methanol. Suitable examples of such polymethylol melamines include trimethylol melamine, trimethoxymethyl melamine, trimethoxymethyl dimethylol melamine, tetramethylol melamine, and hexamethoxymethyl melamine.

Additionally, these materials may be employed with urea formaldehyde resins including their alkylated derivatives, ethylene urea formaldehyde resins, 1,2-propylene urea formaldehyde resins, Lil-propylene urea formaldehyde resins, other cyclic ureas of this type, and their alkylated derivatives.

Still further, these materials may be employed with other textile finishing agents not characterized as aminoplast resins, which may be either thermosetting or thermoplastic. Thus, for example, phenol formaldehyde resins, ketone formaldehyde resins, as for example, acetone formaldehyde resins, epoxy resins, as for example, polyglycidyl ethers of polyhydric alcohols, such as the diglycidyl ether of ethylene glycol, and the like.

Among the thermoplastic resins which may be mentioned are monoor homopolymers or copolymers of acrylates. such as methacrylate, ethylac'rylate, butylacrylate, methylmethacrylate, butylmethacrylate, or copolymers of these or their equivalents with styrene, including ring and chain substituted styrenes, acrylonitrile, polyvinyl chloride, polyvinyl acetate, and the like. In addition, the compositions of this invention may obviously be employed with conventional textile treating agents, such as softeners, stifieners, lubricants, dicyandiamide, and other known treating bath components.

I claim:

1. A process for treating a base containing material selected from the group consisting of material of proteinaceous and cellulosic origin, which comprises applying thereto from 0.1 to 30% on the weight of the base material of a perfluoroguan-amine selected from those having the following formulae:

wherein n is from to 13 inclusive, m is an integer from 1 to 8, inclusive, R to R are selected from the group consisting of H, alkyl having from 1 to 18 carbon atoms, cyclohexyl, allyl, phenyl, chlorophenyl, and CH OR where R is H or lower alkyl containing from 1 to 4 carbon atoms, and curing said compound on the base, employing heat and a catalyst therefor.

2. A process imparting durable insect pest repellent on textile materials containing wool, which comprises applying thereto in an insect repelling amount a perfiuoroguanamine selected from those having the following formulae:

wherein n is from 0 to 13 inclusive, m is from 1 to 8 inclusive, R to R are selected from the group consisting of H, alkyl having from 1 to 18 carbon atoms, cyclohexyl, allyl, phenyl, chlorophenyl and CH OR wherein R is H or lower alkyl containing from 1 to 4 carbon atoms, and curing said compound on the wool-containing material by employing heat and a catalyst therefor.

3. A process for imparting grease and oil repellency to textile materials, which comprises applying thereto in a grease and oil repelling amount a perfluoroguanamine selected from those having the following formulae:

wherein n is from 0 to 13 inclusive, m is from 1 to 8 inclusive, R to R are selected from the group consisting of H, alkyl having from 1 to 18 carbon atoms, cyclohexyl, allyl, phenyl, chlorophenyl and CH OR wherein R is H or lower alkyl containing from 1 to 4 carbon atoms, and curing said compound on the textile material by employing heat and a catalyst therefor.

4. A process according to claim 3, wherein the textile material is cellulosic.

5. Base material containing proteinaceous or cellulosic constituents having thereon from 0.1 to 30% on the weight of the base material of a perfluoroguanamine selected from those having the following formulae:

wherein n is from 0 to 13 inclusive, m is from 1 to 8 inclusive, R to R are selected from the group consisting of H, alkyl having from 1 to 18 carbon atoms, cyclohexyl, allyl, phenyl chlorophenyl, and CH OR where R is H or lower alkyl containing from 1 to 4 carbon atoms.

7. A textile fabric containing proteinaceous fiber, having cured thereon to a water-insoluble state in an amount 20 sufficient to impart grease and oil repellency, a perflu0roguanamine selected from those having the following forrnulae:

wherein n is from 0 to 13 inclusive, m is from 1 to 8 inelusive, R to R are selected from the group consisting of H, alkyl having from 1 to 18 carbon atoms, cyclohexyl, allyl, phenyl chlorophenyl, and CH OR where R is H or lower alkyl containing from 1 to 4 carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 2,385,766 9/1945 Thurston 117139.5X

WILLIAM D. MARTIN, Primary Examiner.

T. G. DAVIS, Assistant Examiner. 

1. A PROCESS FOR TREATING A BASE CONATINING MATERIAL SELECTED FROM THE GROUP CONSISTING OF MATERIAL OF PROTEINACEOUS AND CELLULOSIC ORIGIN, WHICH COMPRISES APPLYING THERETO FROM 0.1 TO 30% ON THE WEIGHT OF THE BASE MATERIAL OF A PERFLUOROGUANAMINE SELECTED FROM THOSE HAVING THE FOLLOWING FORMULAE: 